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The properties of fluids can be significantly altered by the geometry of their confining environments. While there has been significant work on the properties of such confined fluids, the properties of fluids under ultraconfinement, environments where, at least in one plane, the dimensions of the confining environment are similar to that of the confined molecule, have not been investigated. This paper investigates the dynamic properties of water in beryl (BeiAliSifiOis), the structure of which contains approximately 5-Â-diam channels parallel to the c axis. Three techniques, inelastic neutron scattering, quasielastic neutron scattering, and dielectric spectroscopy, have been used to quantify these properties over a dynamic range covering approximately 16 orders of magnitude. Because beryl can be obtained in large single crystals we were able to quantify directional variations, perpendicular and parallel to the channel directions, in the dynamics of the confined fluid. These are significantly anisotropic and somewhat counterintuitively, show that vibrations parallel to the c-axis channels are significantly more hindered than those perpendicular to the channels. The effective potential for vibrations in the c direction is harder than the potential in directions perpendicular to it. There is evidence of single-file diffusion of water molecules along the channels at higher temperatures, but below 150 K this diffusion is strongly suppressed. No such suppression, however, has been observed in the channel-perpendicular direction. Inelastic neutron scattering spectra include an intramolecular stretching O-H peak at ~465 meV. As this is nearly coincident with that known for free water molecules and approximately 30 meV higher than that in liquid water or ice, this suggests that there is no hydrogen bonding constraining vibrations between the channel water and the beryl structure. However, dielectric spectroscopic measurements at higher temperatures and lower frequencies yield an activation energy for the dipole reorientation of 16.4 ± 0.14 kJ/mol, close to the energy required to break a hydrogen bond in bulk water. This may suggest the presence of some other form of bonding between the water molecules and the structure, but the resolution of the apparent contradiction between the inelastic neutron and dielectric spectroscopic results remains uncertain. [ABSTRACT FROM AUTHOR]

Quasielastic neutron scattering (QENS) was used to investigate the diffusion dynamics of hydration water on the surface of futile (TiO2) nanopowder. The dynamics measurements utilizing two inelastic instruments, a backscattering spectrometer and a disk chopper spectrometer, probed the fast, intermediate, and slow motions of the water molecules on the time scale of picoseconds to more than a nanosecond. We employed a model-independent analysis of the data collected at each value of the scattering momentum transfer to investigate the temperature dependence of several diffusion components. All of the probed components were present in the studied temperature range of 230-320 K, providing, at a first sight, no evidence of discontinuity in the hydration water dynamics. However, a qualitative change in the elastic scattering between 240 and 250 K suggested a surface freezing-melting transition, when the motions that were localized at lower temperatures became delocalized at higher temperatures. On the basis of our previous molecular dynamics simulations of this system, we argue that interpretation of QENS data from such a complex interfacial system requires at least qualitative input from simulations, particularly when comparing results from spectrometers with very different energy resolutions and dynamic ranges. [ABSTRACT FROM AUTHOR]

Diverse biological functions of biomembranes are made possible by their rich dynamic behaviors across multiple scales. While the potential coupling between the dynamics of differing scales may underlie the machineries regulating the biomembrane-involving processes, the mechanism and even the existence of this coupling remain an open question, despite the latter being taken for granted. Via inelastic neutron scattering, we examined dynamics across multiple scales for the lipid membranes whose dynamic behaviors were perturbed by configurational changes at two membrane regions. Surprisingly, the dynamic behavior of individual lipid molecules and their collective motions were not always coupled. This suggests that the expected causal relation between the dynamics of the differing hierarchical levels does not exist and that an apparent coupling can emerge by manipulating certain membrane configurations. The findings provide insight on biomembrane modeling and how cells might individually or concertedly control the multiscale membrane dynamics to regulate their functions. [ABSTRACT FROM AUTHOR]

The temperature-dependent diffusivity D(T) of hydrogen solute atoms trapped at dislocations- dislocation pipe diffusion of hydrogen-in deformed polycrystalline PdH, (ϰ ~ 10-3 [H]/ [Pd]) has been quantified with quasielastic neutron scattering between 150 and 400 K. We observe diffusion coefficients for trapped hydrogen elevated by one to two orders of magnitude above bulk diffusion. Arrhenius diffusion behavior has been observed for dislocation pipe diffusion and regular bulk diffusion, the latter in well-annealed poly crystalline Pd. For regular bulk diffusion of hydrogen in Pd we find D(T) = D0exp(-Eα/kT) = 0.005exp(-0.23 eV/kT) cm2/s , in agreement with the known diffusivity of hydrogen in Pd. For hydrogen dislocation pipe diffusion we find D(T) ≃ 10-5exp (-E α/kT ) cm2/s , where Eα = 0.042 and 0.083 eV for concentrations of 0.52 × 10-3 and 1.13 × 10-3 [H]/ [Pd], respectively. Ab initio computations provide a physical basis for the pipe diffusion pathway and confirm the reduced barrier height. [ABSTRACT FROM AUTHOR]

Quasielastic neutron scattering of H2 and D2 in the same nanoporous carbon at 10-40 K demonstrates extreme quantum sieving, with D2 diffusing up to 76 times faster. D2 also shows liquidlike diffusion while H2 exhibits Chudley-Elliott jump diffusion, evidence of their different relationships with the local lattice of adsorption sites due to quantum effects on intermolecular interactions. The onset of diffusion occurs at 22-25 K for H2and 10-13 K for D2. At these temperatures, H2 and D2 have identical thermal de Broglie wavelengths that correlate with the dominant pore size. [ABSTRACT FROM AUTHOR]

The translational dynamics of hydration water confined in calcium-silicate-hydrate (C-S-H) gel was studied by quasielastic neutron scattering spectroscopy in the temperature range from 280 to 230 K. The stretch exponent β, the self-diffusion constant D, the average translational relaxation time <τ>, and the temperature dependence of confinement radius α extracted from the elastic fraction of immobile water molecules p(Q) were obtained from the analyses of the low- Q spectra according to the relaxing cage model. Measurements were made using C-S-H of three different water contents, 10%, 17%, and 30%. Among the three samples of C-S-H gel with different water contents, the values of β decrease with increasing water contents, while α increases. The values of D and <τ> are insensitive to temperature for the two lower water contents, as opposed to the 30% case where a slight variation is observed. The trend for violation of the Stokes-Einstein relation is only visible in the case of 30% water content. [ABSTRACT FROM AUTHOR]

Liu and co-workers [Phys. Rev. Β 82, 161415 (2010)] discussed the long-standing debate regarding whether H20 molecules on the defect-free (110) surface of rutile (α-TiO2) sorb associatively, or there is dissociation of some or all first-layer water to produce hydroxyl surface sites. They conducted static density functional theory (DFT) and DFT molecular dynamics (DFT-MD) investigations using a range of cell configurations and functionals. We have reproduced their static DFT calculations of the influence of crystal slab thickness on water sorption energies. However, we disagree with several assertions made by these authors: (a) that second-layer water structuring and hydrogen bonding to surface oxygens and adsorbed water molecules are "weak"; (b) that translational diffusion of water molecules in direct contact with the surface approaches that of bulk liquid water; and (c) that there is no dissociation of adsorbed water at this surface in contact with liquid water. These assertions directly contradict our published work, which compared synchrotron x-ray crystal truncation rod, second harmonic generation, quasielastic neutron scattering, surface charge titration, and classical MD simulations of rutile (110) single-crystal surfaces and (HO)-dominated powders in contact with bulk water, and (HO)-dominated rutile nanoparticles with several monolayers of adsorbed water. [ABSTRACT FROM AUTHOR]

Dynamics of hydration water is essential for the function of biomacromolecules. Previous studies have demonstrated that water molecules exhibit subdiffusion on the surface of biomacromolecules; yet the microscopic mechanism remains vague. Here, by performing neutron scattering, molecular dynamics simulations, and analytic modeling on hydrated perdeuterated protein powders, we found water molecules jump randomly between trapping sites on protein surfaces, whose waiting times obey a broad distribution, resulting in subdiffusion. Moreover, the subdiffusive exponent gradually increases with observation time towards normal diffusion due to a many-body volume-exclusion effect. [ABSTRACT FROM AUTHOR]

Water is widely assumed to be essential for protein dynamics and function. In particular, the well-documented "dynamical" transition at ~200 K, at which the protein changes from a rigid, nonfunctional form to a flexible, functional state, as detected in hydrogenated protein by incoherent neutron scattering, requires hydration. Here, we report on coherent neutron scattering experiments on perdeuterated proteins and reveal that a transition occurs in dry proteins at the same temperature resulting primarily from the collective heavy-atom motions. The dynamical transition discovered is intrinsic to the energy landscape of dry proteins. [ABSTRACT FROM AUTHOR]

Using neutron scattering and ab initio simulations, we document the discovery of a new "quantum tunneling state" of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. In addition, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state. [ABSTRACT FROM AUTHOR]

Diverse biological functions of biomembranes are made possible by their rich dynamic behaviors across multiple scales. While the potential coupling between the dynamics of differing scales may underlie the machineries regulating the biomembrane-involving processes, the mechanism and even the existence of this coupling remain an open question, despite the latter being taken for granted. Via inelastic neutron scattering, we examined dynamics across multiple scales for the lipid membranes whose dynamic behaviors were perturbed by configurational changes at two membrane regions. Surprisingly, the dynamic behavior of individual lipid molecules and their collective motions were not always coupled. This suggests that the expected causal relation between the dynamics of the differing hierarchical levels does not exist and that an apparent coupling can emerge by manipulating certain membrane configurations. The findings provide insight on biomembrane modeling and how cells might individually or concertedly control the multiscale membrane dynamics to regulate their functions.

Dynamics of hydration water is essential for the function of biomacromolecules. Previous studies have demonstrated that water molecules exhibit subdiffusion on the surface of biomacromolecules; yet the microscopic mechanism remains vague. Here, by performing neutron scattering, molecular dynamics simulations, and analytic modeling on hydrated perdeuterated protein powders, we found water molecules jump randomly between trapping sites on protein surfaces, whose waiting times obey a broad distribution, resulting in subdiffusion. Moreover, the subdiffusive exponent gradually increases with observation time towards normal diffusion due to a many-body volume-exclusion effect.

Water is widely assumed to be essential for protein dynamics and function. In particular, the well-documented "dynamical" transition at ∼200  K, at which the protein changes from a rigid, nonfunctional form to a flexible, functional state, as detected in hydrogenated protein by incoherent neutron scattering, requires hydration. Here, we report on coherent neutron scattering experiments on perdeuterated proteins and reveal that a transition occurs in dry proteins at the same temperature resulting primarily from the collective heavy-atom motions. The dynamical transition discovered is intrinsic to the energy landscape of dry proteins.

The characteristic relaxation time τ of protein hydration water exhibits a strong hydration level h dependence. The dynamic crossover is observed when h is higher than the monolayer hydration level hc=0.2-0.25 and becomes more visible as h increases. When h is lower than hc, τ only exhibits Arrhenius behavior in the measured temperature range. The activation energy of the Arrhenius behavior is insensitive to h, indicating a local-like motion. Moreover, the h dependence of the crossover temperature shows that the protein dynamic transition is not directly or solely induced by the dynamic crossover in the hydration water.

The translational dynamics of hydration water confined in calcium-silicate-hydrate (C-S-H) gel was studied by quasielastic neutron scattering spectroscopy in the temperature range from 280 to 230 K. The stretch exponent β, the self-diffusion constant D, the average translational relaxation time {τ}, and the temperature dependence of confinement radius α extracted from the elastic fraction of immobile water molecules p(Q) were obtained from the analyses of the low-Q spectra according to the relaxing cage model. Measurements were made using C-S-H of three different water contents, 10%, 17%, and 30%. Among the three samples of C-S-H gel with different water contents, the values of β decrease with increasing water contents, while α increases. The values of D and {τ} are insensitive to temperature for the two lower water contents, as opposed to the 30% case where a slight variation is observed. The trend for violation of the Stokes-Einstein relation is only visible in the case of 30% water content.

Quasielastic neutron scattering (QENS) was used to investigate the diffusion dynamics of hydration water on the surface of rutile (TiO(2)) nanopowder. The dynamics measurements utilizing two inelastic instruments, a backscattering spectrometer and a disk chopper spectrometer, probed the fast, intermediate, and slow motions of the water molecules on the time scale of picoseconds to more than a nanosecond. We employed a model-independent analysis of the data collected at each value of the scattering momentum transfer to investigate the temperature dependence of several diffusion components. All of the probed components were present in the studied temperature range of 230-320 K, providing, at a first sight, no evidence of discontinuity in the hydration water dynamics. However, a qualitative change in the elastic scattering between 240 and 250 K suggested a surface freezing-melting transition, when the motions that were localized at lower temperatures became delocalized at higher temperatures. On the basis of our previous molecular dynamics simulations of this system, we argue that interpretation of QENS data from such a complex interfacial system requires at least qualitative input from simulations, particularly when comparing results from spectrometers with very different energy resolutions and dynamic ranges.

Our quasielastic neutron-scattering experiments and molecular-dynamics simulations probing surface water on rutile (TiO2) have demonstrated that a sufficiently high hydration level is a prerequisite for the temperature-dependent crossover in the nanosecond dynamics of hydration water. Below the monolayer coverage of mobile surface water, a weak temperature dependence of the relaxation times with no apparent crossover is observed. We associate the dynamic crossover with interlayer jumps of the mobile water molecules, which become possible only at a sufficiently high hydration level.

We study the dynamic susceptibility chi&#95;{T}(Q,t) of deeply supercooled water by means of quasielastic neutron scattering and molecular dynamics simulations. Both techniques show an increase in the peak height of chi&#95;{T}(Q,t) as the temperature is lowered toward the dynamic crossover temperature T&#95;{L} . Below T&#95;{L} , the peak height decreases steadily. We attribute this phenomenon to the change in slope of the Arrhenius plot of the translational relaxation time at T&#95;{L} . In contrast, the peak height of the calculated four-point correlation function chi&#95;{4}(Q,t) , directly related to the size of dynamic heterogeneity, increases toward and below T&#95;{L} .